Plant disease control composition and its use

ABSTRACT

A composition for controlling plant diseases comprising a tetrazolinone compound represented by a formula (1): 
     
       
         
         
             
             
         
       
     
     wherein n is an integer of any one of 0 to 5; R 1  represents a halogen atom and the like; R 2  represents a C1-C3 alkyl group and the like; the R 1  or R 2  can have independently halogen atom(s) in the alkyl moiety; with the proviso that when n is an integer of 2 or more, two or more of the R 1  may be different from each other, and an carboxamide compound, preferably the composition for controlling plant diseases wherein a weight ratio of the tetrazolinone compound to the carboxamide compound is that of the tetrazolinone compound/the carboxamide compound=0.1/1 to 10/1, shows an excellent controlling efficacy on plant diseases.

TECHNICAL FIELD

This application claims priority to and the benefit of Japanese PatentApplication No. 2013-151419, filed Jul. 22, 2013, the entire contents ofwhich is incorporated herein by reference.

The present invention relates to a plant disease control composition andits use.

BACKGROUND ART

Hitherto, for controlling plant diseases, many compounds have beendeveloped and used practically (see, Patent Literatures 1 and 2).

CITATION LIST Patent Literature

Patent Literature 1: WO 99/05139 pamphlet

Patent Literature 2: WO 2013/092224 pamphlet

SUMMARY OF INVENTION Problems to be Solved by Invention

An object of the present invention is to provide a composition having anexcellent control efficacy on plant diseases.

Means to Solve Problems

The present inventors have intensively studied to find out a compositionhaving an excellent control efficacy on plant diseases. As a result,they have found that a composition for controlling plant diseasescomprising a tetrazolinone compound represented by the following formula(1) and one or more carboxamide compounds selected from thebelow-mentioned Group (A) has an excellent control efficacy on plantdiseases.

Specifically, the present invention includes the followings:

-   [1] A composition for controlling plant diseases comprising a    tetrazolinone compound represented by a formula (1):

wherein

n is an integer of any one of 0 to 5;

R¹ represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group,a C1-C6 alkylthio group, a nitro group or a cyano group;

R² represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogenatom, a C1-C3 alkoxy group, a C1-C2 alkylthio group, a C2-C3 alkenylgroup, or a C2-C3 alkynyl group,

the R¹ or R² can have independently halogen atom(s) in the alkyl moiety;

with the proviso that when n is an integer of 2 or more, two or more ofthe R¹ may be different from each other,

and one or more carboxamide compounds selected from the Group (A):

-   Group (A): a group consisting of bixafen, benzovindiflupyr,    fluxapyroxad, penthiopyrad,    N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylic    acid amide, a compound represented by the following formula (b):

isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen,flutolanil, mepronil, carboxin, thifluzamide, and furametpyr.

-   [2] The composition for controlling plant diseases described in [1]    wherein a weight ratio of the tetrazolinone compound to the    carboxamide compound is that of the tetrazolinone compound/the    carboxamid compound=0.1/1 to 10/1.-   [3] A method for controlling plant diseases which comprises applying    each effective amount of a tetrazolinone compound represented by a    formula (1):

wherein

n is an integer of any one of 0 to 5;

R¹ represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group,a C1-C6 alkylthio group, a nitro group or a cyano group;

R² represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogenatom, a C1-C3 alkoxy group, a C1-C2 alkylthio group, a C2-C3 alkenylgroup, or a C2-C3 alkynyl group,

the R¹ or R² can have independently halogen atom(s) in the alkyl moiety;

with the proviso that when n is an integer of 2 or more, two or more ofthe R¹ may be different from each other,

and one or more carboxamide compounds selected from the Group (A):

-   Group (A): a group consisting of bixafen, benzovindiflupyr,    fluxapyroxad, penthiopyrad,    N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylic    acid amide, a compound represented by the following formula (b):

isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen,flutolanil, mepronil, carboxin, thifluzamide, and furametpyr,to a plant or a soil for cultivating the plant.

-   [4] The method for controlling plant diseases described in [3]    wherein a weight ratio of the tetrazolinone compound to the    carboxamide compound is that of the tetrazolinone compound/the    carboxamide compound=0.1/1 to 10/1.-   [5] The method for controlling plant diseases described in [3] or    [4] wherein the plant or the soil for cultivating the plant is wheat    or the soil for cultivating wheat, respectively.

MODE FOR CARRYING OUT THE INVENTION

A composition for controlling plant diseases (hereinafter, referred toas “composition of the present invention”) comprises a tetrazolinonecompound represented by a formula (1):

[wherein

n, R¹ and R² are the same as defined above, respectively.]

-   (hereinafter referred to as “present tetrazolinone compound”)    and one or more carboxamide compounds selected from the Group (A)    (hereinafter, referred to as “present carboxamide compound”)-   Group (A): a group consisting of bixafen, benzovindiflupyr,    fluxapyroxad, penthiopyrad,    N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylic    acid amide, a compound represented by the following formula (b):

isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen,flutolanil, mepronil, carboxin, thifluzamide, and furametpyr.

The present tetrazolinone is explained.

The substituent(s) as described herein is/are described in detail asbelow-mentioned.

The term “halogen atom” as used herein includes a fluorine atom, achlorine atom, a bromine atom, and an iodine atom.

The term “C1-C6 alkyl group” as used herein represents a straight- orbranched-chain hydrocarbon group having 1 to 6 carbon atoms, andincludes, for example, a methyl group, an ethyl group, a propyl group,an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, a pentyl group, and a hexyl group.

The term “C1-C6 alkoxy group” as used herein may be a straight- orbranched-chain group, and includes, for exa pie, a methoxy group, anethoxy group, a propyloxy group, an isopropyloxy group, a butyloxygroup, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxygroup, a pentyloxy group, and a hexyloxy group.

The term “C1-C6 alkylthio group” as used herein may be a straight- orbranched-chain group, and includes, for example, a methylthio group, anethylthio group, a propylthio group, an isopropylthio group, a butylthiogroup, an isobutylthio group, a sec-butylthio group, a tert-butylthiogroup, a pentylthio group, and a hexylthio group.

The term “C1-C3 alkyl group” as used herein includes a methyl group, anethyl group, a propyl group, and an isopropyl group.

The term “C2-C3 alkenyl group” as used herein includes a vinyl group, a1-propenyl group, and a 2-propenyl group.

The term “C2-C3 alkynyl group” as used herein includes an ethynyl group,a 1-propynyl group, and a 2-propynyl group.

The term “C3-C4 cycloalkyl group” as used herein includes a cyclopropylgroup, and a cyclobutyl group.

The term “C1-C3 alkoxy group” as used herein includes a methoxy group,an ethoxy group, a propyloxy group, and an isopropyloxy group.

The term “C1-C2 alkylthio group” as used herein includes a methylthiogroup, and an ethylthio group.

The phrase of “can have halogen atom(s) in the alkyl moiety” as usedherein means that in the definitions of R¹ and R², the C-C6 alkyl group,C1-C3 alkyl group, C1-C6 alkoxy group, C1-C3 alkoxy group, C1-C6alkylthio group, C1-C2 alkylthio group, and C3-04 cycloalkyl group canhave halogen atom(s).

The C1-C6 alkyl group having halogen atom(s) as used herein includes,for example, a monofluoromethyl group, a difluoromethyl group, atrifluoromethyl group, a monochloromethyl group, a dichloromethyl group,a trichloromethyl group, a dibromomethyl group, a chlorofluoromethylgroup, a dichlorofluoromethyl group, a chlorodifluoromethyl group, a2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethylgroup, a pentafluoroethyl group, a 3-fluoropropyl group, a2,2-difluoropropyl group, a 3,3,3-trifluoropropyl group, aheptafluoropropyl group, a heptafluoroisopropyl group, a1-(trifluoromethyl)-2,2,2-trifluoroethyl group, a 3-fluoropropyl group,a 4-fluorobutyl group, and a 5-fluorohexyl group.

The C1-C3 alkyl group having halogen atom(s) as used herein includes,for example, a fluoromethyl group, a difluoromethyl group, atrifluoromethyl group, a chloromethyl group, a dichloromethyl group, atrichloromethyl group, a dibromomethyl group, a chlorofluoromethylgroup, a dichlorofluoromethyl group, a chlorodifluoromethyl group, a2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethylgroup, a 2-chloroethyl group, a 2,2-dichloroethyl group, a2,2,2-trichloropropyl group, a pentafluoroethyl group, a 3-fluoropropylgroup, a 3,3,3,-trifluoropropyl group, a heptafluoropropyl group, aheptafluoroisopropyl group, and a1-(trifluoromethyl)-2,2,2-trifluoroethyl group, and the others.

The C1-C6 alkoxy group having halogen atom(s) as used herein includes,for example, a fluoromethoxy group, a difluoromethoxy group, atrifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group,a trichloromethoxy group, a dibromomethoxy group, a chlorofluoromethoxygroup, a dichlorofluoromethoxy group, a chlorodifluoromethoxy group, a2-fluoroethoxy group, a 2,2,-difluoroethoxy group, a2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a2,2-dichloroethoxy group, a 2,2,2-trichloroethoxy group, apentafluoroethoxy group, a 3-fluoropropyloxy group, a3,3,3-trifluoropropyloxy group, a heptafluoropropyloxy group, aheptafluoroisopropyloxy group, a1-(trifluoromethyl)-2,2,2-trifluoroethyloxy group, a 3-fluoropropyloxygroup, a 4-fluorobutyloxy group, and a 5-fluorohexyloxy group and theothers.

The C1-C3 alkoxy group having halogen atom(s) includes, for example, afluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group,a chloromethoxy group, a dichloromethoxy group, a trichloromethoxygroup, a dibromomethoxy group, a chlorofluoromethoxy group, adichlorofluoromethoxy group, a chlorodifluoromethoxy group, a2-fluoroethoxy group, a 2,2-difluoroethoxy group, a2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a2,2-dichloroethoxy group, a 2,2,2-trichioroethoxy group, apentafluoroethoxy group, a 3-fluoropropyloxy group, a3,3,3-trifluoropropyloxy group, a heptafluoropropyloxy group, aheptafluoroisopropyloxy group, a1-(trifluoromethyl)-2,2,2-trifluoroethyloxy group, and a3-fluoropropyloxy group, and the others.

The C1-C6 alkylthio group having halogen atom(s) includes, for example,a monofluoromethylthio group, a difluoromethylthio group, atrifluoromethylthio group, a monochloromethylthio group, adichlormethylthio group, a trichloromethylthio group, adibromomethylthio group, a chlorofluoromethylthio group, adichlorofluoromethylthio group, a chlorodifluoromethylthio group, a2-fluoroethylthio group, a 2,2-difluoroethylthio group, a2,2,2-trifluoroethylthio group, a pentafluoroethylthio group, a3-fluoropropylthio group, a 2,2-difluoropropylthio group, a3,3,3-trifluoropropylthio group, a heptafluoropropylthio group, aheptafluoroisopropylthio group, a1-(trifluoromethyl)-2,2,2-trifluoroethylthio group, a 3-fluoropropylthiogroup, a 4-fluorobutylthio group, and a 5-fluorohexylthio group, and theothers.

The C1-C2 alkylthio group having halogen atom(s) includes, for example,a monofluoromethylthio group, a difluoromethylthio group, atrifluoromethylthio group, a monochloromethylthio group, adichloromethylthio group, a trichloromethylthio group, adibromomethylthio group, a chlorofluoromethylthio group, adichlorofluoromethylthio group, a chlorodifluoromethylthio group, a2-fluoroethylthio group, a 2,2-difluoroethylthio group, a2,2,2-trifluoroethylthio group, and a pentafluoroethylthio group, andthe others.

The C3-C4 cycloalkyl group having halogen atom(s) includes, for example,a 2-fluorocyclopropyl group, a 2,2-difluorocyclopropyl group, a2-chloro-2-fluorocyclopropyl group, a 2,2-dichlorocyclopropyl group, a2,2-dibromocyclopropyl group, and a 2,2,3,3-tetrafluorocyclobutyl group,and the others.

First, a process for preparing the present tetrazolinone compound isexplained.

The present tetrazolinone compound may be prepared, for example,according to the below-mentioned processes.

(Process A)

The present tetrazolinone compound may be prepared by reacting acompound represented by a formula (2) (hereinafter referred to asCompound (2)) with a compound represented by a formula (3) (hereinafterreferred to as Compound (3)) in the presence of a base.

[wherein,

n, and R¹ and R² are the same as defined above, respectively, and Z¹represents a leaving group such as a chlorine atom, a bromine atom, oran iodine atom]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; acid amides such asN,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, andN-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate;sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methylethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile,and propionitrile; water; and mixed solvents thereof.

Examples of the base to be used in the reaction include organic basessuch as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine,4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine,diazabicycloundecene, and diazabicyclononene; alkali metal carbonatessuch as lithium carbonate, sodium carbonate, potassium carbonate, andcesium carbonate; alkali metal bicarbonates such as lithium bicarbonate,sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate;alkali metal hydroxides such as lithium hydroxide, sodium hydroxide,potassium hydroxide, and cesium hydroxide; alkali metal halides such assodium fluoride, potassium fluoride, and cesium fluoride; alkali metalhydrides such as lithium hydride, sodium hydride, and potassium hydride;and alkali metal alkoxides such as sodium tert-butoxide, and potassiumtert-butoxide.

In the reaction, Compound (3) is used usually within a range of 1 to 10molar ratio(s), and the base is used usually within a range of 0.5 to 5molar ratio(s), as opposed to 1 mole of Compound (2).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

If necessary, sodium iodide, tetrabutylammonium iodide and the othersmay be added to the reaction, and these compounds are used usuallywithin a range of 0.001 to 1.2 molar ratio(s) as opposed to 1 mole ofCompound (2).

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate the present tetrazolinonecompound. The isolated tetrazolinone compound may be further purified,for example, by chromatography and recrystallization.

(Process B)

The present tetrazolinone compound may be prepared by reacting acompound represented by a formula (4) (hereinafter referred to asCompound (4)) with a compound represented by a formula (5) (hereinafterreferred to as Compound (5)) in the presence of a catalyst and a base.

[wherein,

n, R¹, R² are the same as defined above, respectively, and Z² representsa leaving group such as a chlorine atom, a bromine atom, an iodine atom,a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and ap-toluenesulfonyloxy group, a B(OH)₂, an alkoxyboryl group, or atrifluoroborate (BF₃ ⁻K⁺)]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; acid amides such asN,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, andN-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate;sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methylethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile,and propionitrile; and mixed solvents thereof.

Compound (5) to be used in the reaction can be usually used as acommercially available product. Specific examples include chlorobenzene,bromobenzene, iodobenzene, paradichlorobenzene, 4-chlorobromobenzene,4-chloroidobenzene 4-bromoiodobenzene, phenylboronic acid,4-fluorophenylboronic acid, 4-chlorophenylboronic acid,4-methylphenylboronic acid, and 4-methoxyphenylboronic acid.

Examples of the catalyst to be used in the reaction include copper(I)iodide, copper(II) acetate, palladium(II) acetate,dichlorobis(triphenylphosphine)palladium, tetrakistriphenylphosphinepalladium(0), palladium(II) acetate/triscyclohexylphosphine,bis(diphenylphoshine ferrocenyl)palladium(II) dichloride,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium dimer,aryl(chloro)(1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene)palladium,or palladium(II)acetate/dicyclohexyl(2′,4′,6′-triisopropyibiphenyl-2-yl)phosphine, andtris(dibenzylideneacetone)dipalladium.

Examples of the base to be used in the reaction include organic basessuch as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine,4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine,diazabicycloundecene, and diazabicyclononene; alkali metal carbonatessuch as lithium carbonate, sodium carbonate, potassium carbonate, andcesium carbonate; alkali metal bicarbonates such as lithium bicarbonate,sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate;alkali metal hydroxides such as lithium hydroxide, sodium hydroxide,potassium hydroxide, and cesium hydroxide; alkali metal halides such assodium fluoride, potassium fluoride, and cesium fluoride; alkali metalhydrides such as lithium hydride, sodium hydride, and potassium hydride;alkali metal phosphates such as tripotassium phosphate; and alkali metalalkoxides such as sodium methoxide, sodium ethoxide, sodiumtert-butoxide, and potassium tert-butoxide.

In the reaction, Compound (5) is used usually within a range of 1 to 10molar ratio(s), and the catalyst is used usually within a range of 0.001to 5 molar ratio(s), and the base is used usually within a range of 0.5to 10 molar ratio(s), as opposed to 1 mole of Compound (4).

If necessary, a ligand such as 1,10-phenanthroline,tetramethylenediamine and the others may be added to the reaction, andthese compounds are used usually within a range of 0.001 to 5 molarratio(s) as opposed to 1 mole of Compound (4).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate the present tetrazolinonecompound. The isolated tetrazolinone compound may be further purified,for example, by chromatography and recrystallization.

(Process C)

The present tetrazolinone compound may be prepared by coupling acompound represented by a formula (6) (hereinafter referred as toCompound (6)) (which may be prepared according to the similar method toProcess A) with a compound represented by a formula (7) (hereinafterreferred as to Compound (7)) in the presence of a base and a catalyst.

[wherein

n, R¹ and R² are the same as defined above, respectively, Z³ representsa chlorine atom, a bromine atom, an iodine atom, or atrifluoromethanesulfonyloxy group, and Z⁴ represents a B(OH)₂, analkoxyboryl group, or a trifluoroborate (BF₃ ⁻K⁺).]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; acid amides such asN,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, andN-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate;sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methylethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile,and propionitrile; alcohols such as methanol, ethanol, propanol, andbutanol; water, and mixed solvents thereof.

Organoboron compound (7) to be used in the reaction may be used as acommercially available compound, or may be prepared according to amethod described in a review article of N. Miyaura and A. Suzuki, Chem.Rev. 1995, 95, 2457 and the others. The organoboron compound (7) to beused in the reaction can be prepared, for example, by reacting an iodocompound for R² (R²-I) or a bromo compound for R² (R²-Br) with an alkyllithium (such as butyl lithium), followed by reacting the resultingmixtures with boronate esters to obtain boronate ester derivatives.Also, the boronate ester derivatives obtained in the above-mentionedreaction can be hydrolyzed as needed to the corresponding boronic acidderivatives. Further, according to a method described in a reviewarticle of Molander et al. Acc. Chem. Res. 2007, 40, 275 and the like,the above-mentioned boronate ester derivatives can be fluorinated withpotassium bifluoride and the like to obtain the trifluoroborate saltsBF₃ ⁻K⁺.

Examples of the catalyst to be used in the reaction includepalladium(II) acetate, dichlorobis(tripheny phosphine)palladium,tetrakistriphenylphosphine palladium(0), palladium(II)acetate/triscyclohexylphosphine, bis(diphenylphoshineferrocenyl)palladium(II) dichloride,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium dimer, aryl(chloro)(1,3-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene)palladium orpalladium(II)acetate/dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine, andtris(dibenzylideneacetone)dipalladium and the others.

Examples of the base to be used in the reaction include organic basessuch as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine,4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine,diazabicycloundecene, and diazabicyclononene; alkali metal carbonatessuch as lithium carbonate, sodium carbonate, potassium carbonate, andcesium carbonate; alkali metal bicarbonates such as lithium bicarbonate,sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate;alkali metal hydroxides such as lithium hydroxide, sodium hydroxide,potassium hydroxide, and cesium hydroxide; alkali metal halides such assodium fluoride, potassium fluoride, and cesium fluoride; alkali metalhydrides such as lithium hydride, sodium hydride, and potassium hydride;alkali metal phosphates such as tripotassium phosphate; and alkali metalalkoxides such as sodium methoxide, sodium ethoxide, sodiumtert-butoxide, and potassium tert-butoxide.

In the reaction, Compound (7) is used usually within a range of 1 to 10molar ratio(s), and the base is used usually within a range of 1 to 10molar ratio(s), and the catalyst is used usually within a range of0.0001 to 1 molar ratio(s), as opposed to 1 mole of Compound (6).

The reaction temperature is usually within a range of 0 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate the present tetrazolinonecompound. The isolated tetrazolinone compound may be further purified,for example, by chromatography and recrystallization.

Next, a method for preparing a synthetic intermediate compound of thepresent tetrazolinone compound is explained in detail.

(Reference Process A)

The compound represented by a formula (9) (hereinafter referred to asCompound (9)) may be prepared by reacting the Compound (2) with acompound represented by a formula (8) (hereinafter referred to asCompound (8)) in the presence of a base.

[wherein,

R² and Z¹ are the same as defined above, respectively, and R³ representsa protecting group such as an acetyl, group, a formyl group, a benzoylgroup, a methoxycarbonyl group, an ethoxycarbonyl group, abenzyloxycarbonyl group, and a tert-butoxycarbonyl group.]

The reaction can be carried out according to the above-mentioned processA.

(Reference Process B)

The compound represented by formula (4) may be prepared by treating theCompound (9) with a deprotecting agent.

[wherein,

R² and R³ are the same as defined above, respectively.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include ethers suchas diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyleneglycol dimethylether, anisole, methyl tert-butyl ether, and diisopropyl ether;hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane,toluene, and xylene; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; nitriles such as acetonitrile, andpropionitrile; acid amides such as N,N-dimethylformamide,1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone; sulfoxides suchas dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, andmethyl isobutyl ketone; alcohols such as methanol, ethanol, propanol,and butanol; water; and mixed solvents thereof.

The deprotecting agent to be used in the reaction may be used as a baseor an acid. Examples of the base include organic bases such astriethylamine, pyridine, N-methylmorpholine, N-methylpiperidine,4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine,diazabicycloundecene, and diazabicyclononene, piperidine; alkali metalhydroxides such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, and cesium hydroxide; alkali metal alkoxides such as sodiummethoxide, sodium ethoxide, sodium tert-butoxide, and potassiumtert-butoxide. Examples of the acid include trifluoroacetic acid,hydrochloric acid, and sulfuric acid.

In the reaction, the deprotecting agent is used usually within a rangeof 1 to 100 molar ratio(s) as opposed to 1 mole of Compound (9).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (4). The isolatedCompound (4) may be further purified, for example, by distillation,chromatography and recrystallization.

(Reference Process C)

The compound represented by a formula (11) (hereinafter referred toCompound (11)) may be prepared by reacting a compound represented by aformula (10) (hereinafter referred to as Compound (10)) with anazidation agent.

[wherein,

R² is the same as defined above.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; acid amides such asN,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, andN-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate;sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methylethyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile, andpropionitrile; and mixed solvents thereof.

Examples of the azidation agent to be used in the reaction includeinorganic azides such as sodium azide, barium azide, and lithium azide;and organic azides such as trimethylsilyl azide and diphenylphosphorylazide.

In the reaction, the azidation agent is used usually within a range of 1to 10 molar ratio(s) as opposed to mole of Compound (10).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

If necessary, a Lewis acid such as aluminium chloride and zinc chloridemay be added to the reaction, and these compounds are used usuallywithin a range of 0.05 to 5 molar ratio(s) as opposed to 1 mole ofCompound (10).

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (11). Theisolated Compound (11) may be further purified, for example, bychromatography and recrystallization.

(Reference Process D)

The compound represented by a formula (13) (hereinafter referred to asCompound (13)) may be prepared by reacting the Compound (11) with acompound represented by a formula (12) (hereinafter referred to asCompound (12)) in the presence of a base.

[wherein,

R² is the same as defined above, and Z⁵ represents a leaving group suchas a bromine atom, an iodine atom, a methanesulfonyloxy group, atrifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; acid amides such asN,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, andN-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate;sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methylethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile,and propionitrile; water; and mixed solvents thereof.

Compound (12) to be used in the reaction can be usually used as acommercially available product. Specific examples include alkyl halidessuch as methyl bromide, and methyl iodide; dialkyl sulfates such asdimethyl sulfate; alkyl or aryl sulfates such as methylp-toluenesulfonate, and methyl methanesulfonate.

Examples of the base to be used in the reaction include organic basessuch as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine,4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine,diazabicycloundecene, diazabicyclononene; alkali metal carbonates suchas lithium carbonate, sodium carbonate, potassium carbonate, and cesiumcarbonate; alkali metal bicarbonates such as lithium bicarbonate, sodiumbicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metalhydroxides such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, and cesium hydroxide; alkali metal halides such as sodiumfluoride, potassium fluoride, and cesium fluoride; alkali metal hydridessuch as lithium hydride, sodium hydride, and potassium hydride; andalkali metal alkoxides such as sodium tert-butoxide, and potassiumtert-butoxide.

In the reaction, Compound (12) is used usually within a range of 1 to 10molar ratio(s), and the base is used usually within a range of 0.5 to 10molar ratios, as opposed to 1 mole of Compound (11).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (13). Theisolated Compound (13) may be further purified, for example, bychromatography and recrystallization.

(Reference Process E)

The Compound (2) may be prepared by reacting the Compound (13) with ahalogenating agent.

[wherein,

R² and Z¹ are the same as defined above, respectively.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane,ethyleneglycol dimethyl ether, anisole, methyl tert-butyl ether, anddiisopropyl ether; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, fluorobenzene, difluorobenzene, trifluorobenzene,chlorobenzene, dichlorobenzene, trichlorobenzene,α,α,α-trifluorotoluene, and α,α,α-trichlorotoluene; esters such as ethylacetate, and methyl acetate; ketones such as acetone, methyl ethylketone, and methyl isobutyl ketone; nitriles such as acetonitrile, andpropionitrile; and mixed solvents thereof.

Examples of the halogenating agent to be used in the reaction include achlorinating agent, a brominating agent or iodinating agent such aschlorine, bromine, iodine, sulfuryl chloride, N-chlorosuccinimide,N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, iodosuccinimide,tert-butyl hypochlorite, N-chloroglutarimide, N-bromoglutarimide,N-chloro-N-cyclohexyl-benzenesulfonamide, and N-bromophthalimide.

A radical initiator may be used in the reaction.

Examples of the radical initiator to be used in the reaction includebenzoyl peroxide, azobisisobutyronitrile (AIBN),azobiscyclohexanecarbonitrile, diacylperoxide, dialkylperoxydicarbonate, tert-alkyl peroxyester, monoperoxy carbonate,di(tert-alkylperoxy)ketal, and ketone peroxide.

In the reaction, the halogenating agent is used usually within a rangeof 1 to 10 molar ratio(s), and the radical initiator is used usuallywithin a range of 0.01 to 1 molar ratio(s), as opposed to 1 mole ofCompound (13).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (2-1). Theisolated Compound (2-1) may be further purified, for example, bychromatography and recrystallization.

(Reference Process F)

A compound represented by a formula (15) (hereinafter referred to asCompound (15)) can be prepared by reacting a compound represented by aformula (2-1) wherein R² in a formula (2) represents Z¹ (hereinafterreferred to as Compound (2-1)) with a compound represented by a formula(15) (hereinafter referred to as Compound (15)).

[wherein,

Z¹ is the same as defined above, R⁴ represents a C1-C12 alkyl group or aphenyl group, and M represents sodium, potassium or lithium.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include ethers suchas diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyleneglycol dimethylether, anisole, methyl tert-butyl ether, and diisopropyl ether;hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane,toluene, and xylene; halogenated hydrocarbons such as carbontetrachloride, chloroform, dichloromethane, 1,2-dichloroethane,tetrachloroethane, and chlorobenzene; nitriles such as acetonitrile, andpropionitrile; acid amides such as N,N-dimethylformamide,1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone; sulfoxides suchas dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, andmethyl isobutyl ketone; alcohols such as methanol, ethanol, propanol,and butanol; and mixed solvents thereof.

Examples of Compound (14) include sodium methoxide, sodium ethoxide,sodium n-propoxide, sodium n-butoxide, sodium isopropoxide, sodiumsec-butoxide, sodium tert-butoxide, potassium methoxide, potassiumethoxide, potassium n-propoxide, potassium n-butoxide, potassiumisopropoxide, potassium sec-butoxide, potassium tert-butoxide, potassiummethoxide, and sodium phenoxide.

In the reaction, Compound (14) is used usually within a range of 1 to 10molar ratio(s) as opposed to 1 mole of Compound (2-2).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (15). Theisolated Compound (15) may be further purified, for example, bydistillation, chromatography and recrystallization.

(Reference Process G)

A compound represented by a formula (16) (hereinafter referred to asCompound (16)) can be prepared by reacting Compound (15) and Compound(7) in the presence of a base.

[wherein,

R², R⁴, Z⁴ and Z¹ are the same as defined above, respectively.]

The reaction can be carried out according to the above-mentioned ProcessC.

(Reference Process I)

The Compound (2) can be also prepared by reacting Compound (16) and ahalogenating agent.

[wherein,

R², R⁴ and Z¹ are the same as defined above, respectively.]

The reaction is usually carried out in a solvent.

Examples of the solvent to be used in the reaction include hydrocarbonssuch as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, andxylene; halogenated hydrocarbons such as carbon tetrachloride,chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, andchlorobenzene; ketones such as acetone, methyl ethyl ketone, and methylisobutyl ketone; nitriles such as acetonitrile, and propionitrile;organic acids such as formic acid, acetic acid, and trifluoroaceticacid; water; and mixed solvents thereof.

Examples of the halogenating agent include hydrochloric acid,hydrobromic acid, and hydroiodic acid.

In the reaction, the halogenating agent is used usually within a rangeof 1 or more molar ratio(s) as opposed to 1 mole of Compound (16).

The reaction temperature is usually within a range of −20 to 150° C. Thereaction period of the reaction is usually within a range of 0.1 to 24hours.

When the reaction is completed, the reaction mixtures are extracted withorganic solvent(s), and the resulting organic layers are worked up (forexample, drying and concentration) to isolate Compound (2-1). Theisolated Compound (2-1) may be further purified, for example, bydistillation, chromatography and recrystallization.

The present carboxamide compounds are all known compounds, and they aredescribed in “THE PESTICIDE MANUAL-16th EDITION (published by BCPC) ISBN9781901396867”, WO 2011/162397, WO 2006/016708, or WO 2007/072999. Thesecompounds may be obtained from commercially available formulations ormay be prepared according to known methods.

Examples of an embodiment ofN-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylicacid amide as described herein include a compound represented by aformula (a1):

and/or a compound represented by formula (a2):

The present carboxamide compounds are shown in [Table 1] below.

TABLE 1 Compound Present carboxamide compound Compound I bixafenCompound II benzovindiflupyr Compound III fluxapyroxad Compound IVboscalid Compound V compound represented by formula (a1) Compound VIcompound represented by formula (b) Compound VII isofetamid orN-[1,1-dimethyl-2-(4-isopropoxy-o- tolyl)-2-oxoethyl]-3-methylthiophene-2-carboxamide Compound VIII isopyrazam Compound IX penthiopyrad CompoundX fluopyram Compound XI sedaxane Compound XII penflufen Compound XIIIflutolanil Compound XIV mepronil Compound XV carboxin Compound XVIthifluzamide Compound XVII furametpyr Compound XVIII compoundrepresented by formula (a2)

In the composition of the present invention, a weight ratio of thepresent tetrazolinone compound to the present carboxamide compoundincludes, for example, the present tetrazolinone compound/the presentcarboxamide compound=0.01/1 to 500/1, 0.1/1 to 10/1, and 0.1/1 to 3/1,and preferably 0.3/1 to 3/1.

The composition of the present invention may be a mixture as itself ofthe present tetrazolinone compound and the present carboxamide compound,and is usually prepared by mixing the present tetrazolinone compound,the present carboxamide compound and an inert carrier, optionally addinga surfactant and other auxiliaries for formulation.

The composition of the present invention may be formulated into an oilsolution, an emulsifiable concentrate, a flowable formulation, awettable powder, a water dispersible granule, a dust, or a granule. Thethus formulations can be used directly as a plant disease control agent,or used after the addition of other inert ingredients.

The total amount of the present tetrazolinone compound and the presentcarboxamide compound in the composition of the present invention isusually within a range from 0.1% to 99% by weight, preferably from 0.2%to 90% by weight, and more preferably from 1% to 80% by weight.

Examples of the solid carrier to be used in the formulation includeclays (for example, kaolin, diatomaceous earth, synthetic hydratedsilicon dioxide, Fubasami clay, bentonite and acid clay), talcs or theother inorganic minerals (for example, sericite, quartz powder, sulfurpowder, activated charcoal, calcium carbonate and hydrated silica) inthe form of fine powders or particulates, and examples of the liquidcarrier include water, alcohols (for example, methanol and ethanol),ketones (for example, acetone and methyl ethyl ketone), aromatichydrocarbons (for example, benzene, toluene, xylene, ethylbenzene andmethyl naphthalene), aliphatic hydrocarbons (for example, n-hexane,cyclohexane and kerosene), esters (for example, ethyl acetate and butylacetate), nitriles (for example, acetonitrile and isobutyronitrile),ethers (for example, dioxane and diisopropylether), acid amides (forexample, DMF and dimethylacetamide), halogenated hydrocarbons (forexample, dichloroethane, trichloro ethylene and carbon tetrachloride)and the others.

Examples of the surfactants include alkyl sulfates, alkyl sulfonates,alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenatedcompounds thereof, polyethylene glycol ethers, polyol esters and sugaralcohol derivatives.

Examples of other auxiliary agents for formulation include a sticker, adispersant and a stabilizer, and specific examples include casein,gelatin, polysaccharides (for example, starch, gum arabic, cellulosederivatives and alginic acid), lignin derivatives, bentonite, sugars,water-soluble synthetic polymers (for example, polyvinyl alcohol,polyvinyl pyrrolidone and polyacrylic acids), PAP (acidic isopropylphosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils, mineral oils, fatty acids or fatty acid esters thereofand the others.

The composition of the present invention may be also formulated byformulating each of the present tetrazolinone compound and the presentcarboxamide compound according the above-mentioned method and ifnecessary, diluting it with water to obtain a formulation containing thepresent tetrazolinone compound or diluted solutions containing the same,or a formulation containing the present carboxamide compound or dilutedsolutions containing the same, respectively, followed by mixing theresulting formulations or diluted solutions to each other.

The composition of the present invention can be used to protect plantsfrom plant diseases.

The control method of the present invention can control plant diseasesby applying the composition of the present invention to plants or soilfor cultivating plants, alternatively by applying the presenttetrazolinone compound or the present carboxamide compound separately toplants or soil for cultivating plants.

The method for applying the composition of the present invention is notparticularly limited, as far as the applying form is a form by which thepresent compound may be applied substantially, and includes, forexample, an application to plants such as a foliar application; anapplication to area for cultivating plants such as a submergedtreatment; and an application to seed such as seed disinfection.

The application dose of the composition of the present invention variesdepending on weather conditions, dosage forms, timing of application,methods of application, areas to be applied, target diseases, targetcrops and the others, and is in the range of usually from 1 to 500 g,and preferably from 2 to 200 g per 1,000 m² of the area to be applied.The emulsifiable concentrate, the wettable powder or the suspensionconcentrate etc., is usually applied by diluting it with water. In thiscase, the concentration of the composition of the present inventionafter dilution is in the range of usually 0.0005 to 2% by weight, andpreferably 0.005 to 1% by weight, and the dust formulation or thegranular formulation etc., is usually applied as itself without dilutingit. In the application to seeds, the amount of the composition of thepresent invention is in the range of usually from 0.001 to 100 g, andpreferably from 0.01 to 50 g per 1 kg of the seeds.

Examples of the place where the plant diseases grow include paddyfields, fields, tea gardens, orchards, non-agricultural lands, houses,nursery trays, nursery boxes, nursery soils and nursery bed.

The composition of the present invention can be used as agent forcontrolling plant disease in agricultural lands such as fields, paddyfields, lawns, and orchards. The composition of the present inventioncan control diseases occurred in the agricultural lands or the othersfor cultivating the following “plant” and the others.

Crops:

-   corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean,    peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco,    and the others;

Vegetables:

-   solanaceous vegetables (for example, eggplant, tomato, pimento,    pepper and potato),-   cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini,    water melon and melon),-   cruciferous vegetables (for example, Japanese radish, white turnip,    horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard,    broccoli, cauliflower),-   asteraceous vegetables (for example, burdock, crown daisy, artichoke    and lettuce),-   liliaceous vegetables (for example, green onion, onion, garlic and    asparagus),-   ammiaceous vegetables (for example, carrot, parsley, celery and    parsnip),-   chenopodiaceous vegetables (for example, spinach and Swiss chard),-   lamiaceous vegetables (for example, Perilla frutescens, mint and    basil),-   strawberry, sweet potato, Dioscorea japonica, colocasia and the    others;

Flowers:

Ornamental foliage plants:

Fruits:

-   pomaceous fruits (for example, apple, pear, Japanese pear, Chinese    quince and quince),-   stone fruits (for example, peach, plum, nectarine, Prunus mume,    cherry fruit, apricot and prune),-   citrus fruits (for example, Citrus unshiu, orange, lemon, lime and    grapefruit),-   nuts (for example, chestnut, walnuts, hazelnuts, almond, pistachio,    cashew nuts and macadamia nuts),-   berry fruits (for example, blueberry, cranberry, blackberry and    raspberry),-   grapes, kaki persimmon, olive, Japanese plum, banana, coffee, date    palm, coconuts, and the others;

Trees other than fruit trees:

-   tea, mulberry, flowering plant,-   roadside trees (for example, ash, birch, dogwood, Eucalyptus, Ginkgo    biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar    formosana, plane tree, zelkova, Japanese arborvitae, fir wood,    hemlock, juniper, Pinus, Picea, and Taxus cuspidate); and the    others.

The above-mentioned “plant” includes genetically modified crops.

The pests on which the composition of the present invention has acontrol efficacy include plant pathogens such as filamentous fungus, andspecifically include the following examples, but are not limitedthereto.

Rice diseases: blast (Magnaporthe grisea), brown spot (Cochliobolusmiyabeanus), sheath blight (Rhizoctonia solani), and bakanae disease(Gibberella fujikuroi);

Wheat diseases: powdery mildew (Erysiphe graminis), fusarium blight(Fusarium gaminearum, F. avenaceum, F. culmorum, Microdochium nivale),rust (Puccinia striiformis, P. graminis, P. recondita), snow mould(Micronectriella nivale), typhulasnow blight (Typhula sp.), loose smut(Ustilago tritici), stinking smut (Tilletia caries), eyespot(Pseudocercosporella herpotrichoides), leaf blotch (Mycosphaerellagraminicola), glume blotch (Stagonospora nodorum), tan spot (Pyrenophoratritici-repentis);

Barly diseases: powdery mildew (Erysiphe graminis), fusarium blight(Fusarium gaminearum, F. avenaceum, F. culmorum, Microdochium nivale),rust (Puccinia striiformis, P. graminis, P. hordei), loose smut(Ustilago nuda), scald (Rhynchosporium secalis), net blotch (Pyrenophorateres), spot blotch (Cochliobolus sativus), leaf stripe (Pyrenophoragraminea), and rhizoctonia seeding blight (Rhizoctonia solani);

Corn diseases: smut (Ustilago maydis), southern leaf blight(Cochliobolus heterostrophus), Zonate leaf spot (Gloeocercosporasorghi), southern rust (Puccinia polvsora), gray leaf spot (Cercosporazeae-maydis), and rhizoctonia seeding blight (Rhizoctonia solani);

Citrus diseases: melanose (Diaporthe citri), scab (Elsinoe fawcetti),fruit rot (Penicillium digitatum, P. italicum); Phytophthora diseases(Phytophthora parasitica, Phytophthora citrophthora);

Apple diseases: blossom blight (Monilinia mali), canker (Valsaceratosperma), powdery mildew (Podosphaera leucotricha), alternaria leafspot (Alternaria alternata apple pathotype), scab (Venturia inaequalis),bitter rot (Colletotrichum acutatum), and crown rot (Phytophtoracactorum);

Pear diseases: scab (Venturia nashicola, V. pirina), black spot(Alternaria alternata Japanese pear pathotype), rust (Gymnosporangiumharaeanum), and phytophthora fruit rot (Phytophtora cactorum);

Peach diseases: brown rot (Monilinia fructicola), scab (Cladosporiumcarpophilum) and Phomopsis rot (Phomopsis sp.);

Grapes diseases: anthracnose (Elsinoe ampelina), ripe rot (Glomerellacingulata), powdery mildew (Uncinula necator), rust (Phakopsoraampelopsidis), black rot (Guignardia bidwellii), and downy mildew(Plasmopara viticola);

Diseases of Japanese persimmon: anthracnose (Gloeosporium kaki), andleaf spot (Cercospora kaki, Mycosphaerella nawae);

Diseases of gourd family: anthracnose (Colletotrichum lagenarium),powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerellamelonis), fusarium wilt (Fusarium oxysporum), downy mildew(Pseudoperonospora cubensis), phytophthora rot (Phytophthora sp.), anddamping-off (Pythium sp.);

Tomato diseases: early blight (Alternaria solani), leaf mold(Cladosporium fulvum), and late blight (Phytophthora infestans);

Eggplant disease: brown spot (Phomopsis vexans), and powdery mildew(Erysiphe cichoracearum);

Diseases of Cruciferous Vegetables: alternaria leaf spot (Alternariajaponica), white spot (Cercosporella brassicae), clubroot(Plasmodiophora brassicae), and downy mildew (Peronospora parasitica);

Welsh onion diseases: rust (Puccinia allii) and downy mildew(Peronospora destructor);

Soybean diseases: purple stain (Cercospora kikuchii), sphaceloma scad(Elsinoe glycines), pod and stem blight (Diaporthe phaseolorum var.sojae), septoria brown spot (Septoria glycines), frog eye leaf spot(Cercospora sojina), rust (phakopsora pachyrhizi), phytophthora root andstem rot (Phytophthora sojae), rhizoctonia aerial blight (Rhizoctoniasolani), target spot (Corynespora cassiicola), and sclerotinia stem rot(Sclerotinia sclerotiorum);

Kindney bean diseases: anthracnose (Colletotrichum lindemthianum);

Peanut diseases: early leaf spot (Cercospora personata), late leaf spot(Cercospora arachidicola), and southern blight (Sclerotium rolfsii);

Garden pea diseases: powdery mildew (Erysiphe pisi);

Potato diseases: early blight (Alternaria solani), late blight(Phytophthora infestans), Pink rot (Phytophthora Erythroseptica), andpowdery scab (Spongospora subterranean f. sp. subterranea);

Strawberry diseases: powdery mildew (Sphaerotheca humuli), andanthracnose (Glomerella cingulata);

Tea diseases: net blister blight (Exobasidium reticulatum), white scab(Elsinoe leucospila), gray blight (Pestalotiopsis sp.) and anthracnose(Colletotrichum theaesinensis);

Tabacco diseases: brown spot (Alternaria longipes), powdery mildew(Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downymildew (Peronospora tabacina), and black shank (Phytophthoranicotianae);

Rapeseed diseases: sclerotinia rot (Sclerotinia sclerotiorum), andrhizoctonia seeding blight (Rhizoctonia solani);

Cotton diseases: rhizoctonia seeding blight (Rhizoctonia solani);

Sugar beet diseases: cercospora leaf spot (Cercospora beticola), leafblight (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris),and aphanomyces root rot (Aphanomyces cochlioides);

Rose diseases: black spot (Diplocarpon rosae), powdery mildew(Sphaerotheca pannosa), and downy mildew (Peronospora sparsa);

Diseases of Chrysanthemum: downy mildew (Bremia lactucae), leaf blight(Septoria chrysanthemi-indici), and white rust (Puccinia horiana), leafblight (Septoria chrysanthemi-indici), and white rust (Pucciniahoriana);

Various crops diseases: diseases caused by Pythium spp. (Pythiumaphanidermatum, Pythium debarianum, Pythium irregulare, and Pythiumultimum), gray mold (Botrytis cinerea), and sclerotinia rot (Sclerotiniasclerotiorum);

Diseases of Japanese radish: alternaria leaf spot (Alternariabrassicicola);

Turfgrass diseases: dollar spot (Sclerotinia homeocarpa), brown patchand large patch (Rhizoctonia solani);

Banana diseases: Sigatoka disease (Mycosphaerella fijiensis,Mycosphaerella musicola);

seed diseases or diseases in the early stages of the growth of variousplants caused by caused by Aspergillus spp., Penicillium spp., Fusariumspp., Gibberella spp., Tricoderma spp., Thielaviopsis spp., Rhizopusspp., Mucor spp., Corticium spp., Phoma spp., Rhizoctonia spp. orDiplodia spp.; and

viral diseases of various plants mediated by Polymixa spp. or Olpidiumspp.; and so on.

EXAMPLES

Next, the following Process for the present tetrazolinone compound, andthe Examples including Formulation examples and Test examples, serve toillustrate the present invention in more detail, which should not intendto limit the present invention.

First, Preparation Example for the present tetrazolinone compound isshown.

Preparation Example 1

A mixture of1-(2-bromomethyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation example 3) 1.21 g,1-(4-chlorophenyl)-1H-pyrazole-3-ol 0.78 g, potassium carbonate 0.66 gand acetonitrile 30 mL was stirred with heating under reflux for fourhours. To the reaction mixture after standing to cool was added water,and the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 1) 0.61 g.

Present tetrazolinone Compound 1

¹H-NMR (CDCl₃) δ(ppm): 7.64 (1H, d, J=2.7 Hz), 7.62-7.60 (1H, m),7.53-7.49 (2H, m), 7.45 (1H, t, J=8.0 Hz), 7.39-7.35 (3H, m), 5.80 (1H,d, J=2.7 Hz), 5.54 (2H, s), 3.61 (3H, s).

Preparation Example 2

A mixture of1-(2-bromomethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 6) 18.5 g,1-(4-chlorophenyl)-1H-pyrazole-3-ol 10.4 g, potassium carbonate 8.8 gand acetonitrile 400 mL was stirred with heating under reflux for fourhours. To the reaction mixtures after standing to cool was added waterand the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 2) 24.6 g.

Present Tetrazolinone Compound 2

¹H-NMR (CDCl₃) δ(ppm): 7.81-7.79 (1H, m), 7.65 (1H, d, J=2.4 Hz),7.54-7.50 (2H, m), 7.42-7.35 (4H, m), 5.81 (1H, d, J=2.4 Hz), 5.53 (2H,s), 3.60 (3H, s).

Preparation Example 3

A mixture of the present tetrazolinone compound 2 (described inPreparation Example 2) 0.92 g, methyl boronic acid 0.18 g, tripotassiumphosphate 1.27 g, water 0.11 mL,[1,1′-bis(diphenylphosphino)ferrocene]-palladium(II) dichloridedichloromethane complex 0.16 g, and dioxane 7 mL was stirred withheating under reflux for one and a half hours. To the reaction solutionafter cooling was added water, and the mixtures were extracted withethyl acetate. The organic layer was washed with water and saturatedsaline, dried over magnesium sulfate, and then concentrated underreduced pressure. The resulting residue was subjected to a silica gelcolumn chromatography to give1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 3) 0.27 g.

Present tetrazolinone Compound 3

¹H-NMR (CDCl₃) δ(ppm): 7.64 (1H, d, J=2.7 Hz), 7.52-7.49 (2H, m),7.42-7.35 (4H, m), 7.27-7.24 (1H, m), 5.82 (1H, d, J=2.7 Hz), 5.33 (2H,s), 3.63 (3H, s), 2.56 (3H, s).

Preparation Example 4

A mixture of1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 12) 0.30 g,1-(4-methoxyphenyl)-1H-pyrazole-3-ol 0.21 g, potassium carbonate 0.19 gand acetonitrile 10 ml was stirred with heating under reflux for twohours. To the reaction mixtures after standing to cool was added water,and the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-(4-methoxyphenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 4) 0.28 g.

Present tetrazolinone Compound 4

¹H-NMR (CDCl₃) δ(ppm): 7.57 (1H, d, J=2.7 Hz), 7.49-7.44 (2H, m),7.39-7.36 (2H, m), 7.27-7.23 (1H, m), 6.96-6.91 (2H, m), 5.77 (1H, d,J=2.7 Hz), 5.32 (2H, s) , 3.83 (3H, s), 3.61 (3H, s), 2.56 (3H, s).

Preparation Example 5

A mixture of1-(2-bromomethyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Exmaple 9) 1.20 g,1-(4-chlorophenyl)-1H-pyrazole-3-ol 0.78 g, potassium carbonate 0.66 g,and acetonitrile 30 mL was stirred with heating under reflux for fourhours. To the reaction mixtures after standing to cool was added waterand the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 5) 0.97 g.

Present tetrazolinone Compound 5

¹H-NMR (CDCl₃) δ(ppm): 7.63 (1H, d, J=2.7 Hz), 7.53-7.49 (2H, m), 7.46(1H, dd, J=8.5, 8.0 Hz), 7.38-7.34 (2H, m), 7.08 (1H, d, J=8.5 Hz), 7.04(1H, d, J=8.0 Hz), 5.80 (1H, d, J=2.7 Hz), 5.43 (2H, s), 3.92 (3H, s),3.57 (3H, s).

Preparation Example 6

A mixture of present tetrazolinone compound 2 (described in PreparationExample 2) 0.92 g, ethyl boronic acid 0.22 g, tripotassium phosphate1.27 g, water 0.11 mL,[1,1′-bis(diphenylphosphino)ferrocene]-palladium(II) dichloridedichloromethane complex 0.16 g and dioxane 15 mL was stirred withheating under reflux for two hours. To the reaction solution aftercooling was added water, and the mixtures were extracted with ethylacetate. The organic layers were washed with water and saturated saline,dried over anhydrous magnesium sulfate, and then concentrated underreduced pressure. The resulting residue was subjected to ,a silica gelcolumn chromatography to give1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}3-ethylpenyl)-4-methyl-1,4-dihydroteterazole-5-one(hereinafter referred to as Present tetrazolinone compound 6) 0.24 g.

Present tetrazolinone Compound 6

¹H-NMR (CDCl₃) δ(ppm): 7.65 (1H, d, J=2.7 Hz), 7.53-7.49 (2H, m),7.47-7.42 (2H, m), 7.39-7.35 (2H, m), 7.27-7.24 (1H, m), 5.81 (1H, d,J=2.7 Hz), 5.34 (2H, s), 3.61 (3H, s), 2.90 (2H, q, J=7.6 Hz), 1.30 (3H,t, J=7.6 Hz).

Preparation Example 7

A mixture of present tetrazolinone compound 2 (described in PreparationExample 2) 0.92 g, cyclopropyl boronic acid 0.26 g, tripotassiumphosphate 1.27 g, water 0.11 mL,[1,1′-bis(diphenylphosphino)]ferrocene]-palladium(II) dichloridedichloromethane complex 0.16 g, and dioxane 7 mL was stirred withheating under reflux for one and a half hours. To the reaction solutionafter cooling was added water, and the mixtures were extracted withethyl acetate. The organic layers were washed with water and saturatedsaline, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The resulting residue was subjected to to asilica gel column chromatography to give1-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-cyclopropylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 7) 0.35 g.

Present tetrazolinone Compound 7

¹H-NMR (CDCl₃) δ(ppm): 7.63 (1H, d, J=2.7 Hz), 7.51-7.46 (2H, m),7.41-7.37 (1H, m), 7.36-7.32 (2H, m), 7.24-7.21 (2H, m), 5.80 (1H, d,J=2.7 Hz), 5.53 (2H, s), 3.58 (3H, s), 2.26-2.19 (1H, m), 1.03-0.99 (2H,m), 0.78-0.74 (2H, m).

Preparation Example 8

A mixture of1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 12) 0.30 g,1-(4-bromophenyl)-1H-pyrazole-3-ol 0.27 g, potassium carbonate 0.19 g,and acetonitrile 10 mL was stirred with heating under reflux for fourhours. To the reaction mixtures after standing to cool was added water,and the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-(4-bromophenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methylpheny)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 8) 0.37 g.

Present tetrazolinone Compound 8

¹H-NMR (CDCl₃) δ(ppm): 7.64 (1H, d, J=2.4 Hz), 7.53-7.49 (2H, m),7.45-7.37 (4H, m), 7.27-7.24 (1H, m), 5.82 (1H, d, J=2.4 Hz), 5.33 (2H,s), 3.62 (3H, s), 2.55 (3H, s).

Preparation Example 9

A mixture of1-(2-{[1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 14) 0.49 g,4-chloro-3-flurophenylboronic acid 0.33 g, copper(II) acetate 0.51 g,pyridine 0.28 g, molecular sieve 4A 1.00 g, and acetonitrile 10 mL wasstirred with heating under reflux for forty eight hours. To the reactionmixtures after standing to cool was added water, and the mixtures wereextracted with ethyl acetate. The organic layers were washed with waterand saturated saline, dried over anhydrous magnesium sulfate, and thenconcentrated under reduced pressure. The resulting residue was subjectedto a silica gel column chromatography to give1-(2-{[1-(4-chloro-3-fluorophenyl)-1H-pyrazol-3yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(hereinafter referred to as Present tetrazolinone compound 9) 0.12 g.

Present tetrazolinone Compound 9

¹H-NMR (CDCl₃) δ(ppm): 7.64 (1H, d, J=2.7 Hz), 7.44-7.38 (4H, m),7.28-7.23 (2H, m), 5.84 (1H, d, J=2.7 Hz), 5.33 (2H, s), 3.65 (3H, s),2.56 (3H, s).

Preparation Example 10

A mixture of1-(2-bromomethyl-3-methylpenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 12) 0.30 g,1-(2-methoxyphenyl)-1H-pyrazole-3-ol 0.20 g, potassium carbonate 0.19 gand acetonitrile 10 mL was stirred with heating under reflux for fourhours. To the reaction mixtures after standing to cool was added water,and the mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography togive1-(2-{[1-(2-methoxyphenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydroteterazole-5-one(hereinafter referred to as Present tetrazolinone compound 10) 0.23 g.

Present tetrazolinone Compound 10

¹H-NMR (CDCl₃) δ(ppm): 7.89 (1H, d, J=2.5 Hz), 7.70 (1H, dd, J=8.0, 1.6Hz), 7.41-7.37 (2H, m), 7.26-7.18 (2H, m), 7.06-6.99 (2H, m), 5.76 (1H,d, J=2.5 Hz), 5.32 (2H, s), 3.88 (3H, s), 3.61 (3H, s), 2.55 (3H, s).

Preparation Example 11

A mixture of1-(2-{[1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydroteterazole-5-one(described in Reference Preparation Example 14) 1.00 g,4-chloro-2-methoxyphenyl boronic acid 0.78 g, copper(II) acetate 0.98 g,pyridine 0.59 mL, molecular sieve 4A 1.50 g, and acetonitrile 15 mL wasstirred with heating under reflux for fifteen hours. To the reactionmixtures after standing to cool was added water, and the mixtures wereextracted with ethyl acetate. The organic layers were washed with waterand saturated saline, dried over anhydrous magnesium sulfate, and thenconcentrated under reduced pressure. The resulting residue was subjectedto a silica gel column chromatography to give1-(2-{[1-(4-chloro-2-methoxyphenyl)-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydroteterazole-5-one(hereinafter referred to as Present tetrazolinone compound 11) 0.15 g.

Present tetrazolinone Compound 11

¹H-NMR (CDCl₃) δ: 7.87 (1H, d, J 32 2.5 Hz), 7.65 (1H, d, J=8.5 Hz),7.42-7.37 (2H, m), 7.26-7.24 (1H, m), 7.03 (1H, dd, J 32 8.5, 2.3 Hz),6.99 (1H, d, J=2.3 Hz), 5.77 (1H, d, J=2.5 Hz), 5.30 (2H, s), 3.89 (3H,s), 3.63 (3H, s), 2.55 (3H, s).

Next, processes for preparing intermediates of the above-mentionedPresent tetrazolinone compound are shown below as Reference PreparationExamples.

Reference Preparation Example 1

Anhydrous aluminium chloride 21.9 g was added to N,N-dimethylformamide250 mL under ice-cooling, and the mixtures were stirred for fifteenminutes. Thereto was added sodium azide 10.7 g and the mixtures werestirred for fifteen minutes. Thereto was then added1-chloro-3-isocyanato-2-methylbenzene 25.0 g, and the resulting mixtureswere heated at 80° C. for five hours. The reaction solutions aftercooling were added to a mixture of sodium nitrite 35 g, water 2 L andice 500 g with stirring. The mixtures were acidified with 10%hydrochloric acid and were extracted with ethyl acetate. The organiclayers were washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure to give1-(2-methyl-3-chlorophenyl)-1,4-dihydrotetrazole-5-one 17.0 g.

1-(2-methyl-3-chlorophenyl)-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 2.32 (3H, s), 7.28-7.36 (2H, m), 7.57 (1H, dd,J=6.8, 2.2 Hz), 13.08 (1H, s).

Reference Preparation Example 2

To a mixture of 1-(2-methyl-3-chlorophenyl)-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 1) 10.00 g andN,N-dimethylformamide 100 mL was added 60% sodium hydride 2.30 g underice-cooling. The mixtures were raised to room temperature and werestirred for one hour. To the reaction mixtures was added methyl iodide3.2 mL under ice cooling. The mixtures were raised to room temperatureand stirred for fourteen hours. To the reaction mixtures was addedwater, and the mixtures were extracted with ethyl acetate. The organiclayers were washed with 10% hydrochloric acid, water and saturatedsaline, and was dried over anhydrous magensium sulfate, and thenconcentrated under reduced pressure. The resulting residue was subjectedto a silica gel column chromatography to give1-(2-methyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one 1.56 g.

1-(2-methyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 2.30 (3H, s), 3.73 (3H, s) , 7.27 (1H, d, J=2.7Hz), 7.28 (1H, d, J=7.1 Hz), 7.52 (1H, dd, J=2.7, 6.8 Hz).

Reference Preparation Example 3

A mixture of1-(2-methyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Example 2) 1.56 g,1,1′-azobis(cyclohexane-1-carbonitrile) 0.34 g, N-bromosuccinimide 1.42g and chlorobenzene 30 mL was stirred with heating under reflux for fivehours. To the reaction solutions after cooling was added water, and themixtures were extracted with ethyl acetate. The organic layers werewashed with water and saturated saline, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The resultingresidue was subjected to a silica gel column chromatography to give1-(2-bromomethyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one1.94 g.

1-(2-bromomethyl-3-chlorophenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 3.76 (3H, s), 4.69 (2H, s), 7.35 (1H, dd, J=1.2,8.1 Hz), 7.43 (1H, t, J=8.1 Hz), 7.58 (1H, dd, J=1.2, 8.1 Hz).

Reference Preparation Examples 4

Anhydrous aluminium chloride 19.7 g was added to N,N-dimethylformamide220 mL under ice-cooling, and the mixture was stirred for fifteenminutes. Thereto was added sodium azide 9.6 g and the mixtures werestirred for fifteen minutes. Thereto was then added1-bromo-3-isocyanato-2-methylbenzene 30.3 g and the resulting mixtureswere heated at 80° C. for five hours. The reaction solutions aftercooling were added to a mixture of sodium nitrite 33 g, water 2 L andice 500 g with stirring. The mixtures were acidified with 10%hydrochloric acid, and were extracted with ethyl acetate. The organiclayers were washed with water and saturated saline and then were driedover anhydrous magnesium sulfate and were then concentrated underreduced pressure to give1-(2-methyl-3-bromophenyl)-1,4-dihydrotetrazole-5-one 31.4 g.

1-(2-methyl-3-bromophenyl)-1,4-dihydrotetrazole-5-one

¹H-NMR (DMSO-d₆) δ(ppm): 2.22 (3H, s), 7.34 (1H, t, J=7.2 Hz), 7.49 (1H,dd, J=8.2, 1.1 Hz), 7.82 (1H, dd, J=8.0, 1.0 Hz), 14.72 (1H, s).

Reference Preparation Example 5

To a mixture of 1-(2-methyl-3-bromophenyl)-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 4) 31.40 g andN,N-dimethylformamide 250 mL was added 60% sodium hydride 5.90 g underice-cooling. The reaction mixtures were raised to room temperature, andwere stirred for one hour. To the reaction mixtures was added methyliodide 8.4 mL under ice-cooling. The mixtures were raised to roomtemperature, and were stirred for fourteen hours. To the reactionmixtures was added water and the mixtures were extracted with ethylacetate. The organic layers were washed with 10% hydrochloric acid,water and saturated saline, and dried over anhydrous magnesium sulfateand then concentrated under reduced pressure. The resulting residueswere subjected to a silica gel column chromatography to give1-(2-methyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one 8.47 g.

1-(2-methyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 2.33 (3H, s), 3.73 (3H, s), 7.21 (1H, dt, J=0.5,7.8 Hz), 7.30 (1H, dd, J=1.0, 8.0 Hz), 7.71 (1H, dd, J=1.2, 8.3 Hz).

Reference Preparation Example 6

To a mixture of1-(2-methyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 5) 8.47 g,1,1′-azobis(cyclohexane-1-carbonitrile) 1.54 g, N-bromosuccinimide 6.44g and chlorobenzene 125 mL was stirred with heating under reflux forfive hours. To the reaction solutions after cooling was added water andthe resulting mixtures were extracted with ethyl acetate. The organiclayers were washed with water and saturated saline, and dried overanhydrous magnesium sulfate and then concentrated under reducedpressure. The resulting residues were subjected to a silica gel columnchromatography to give1-(2-bromomethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one 7.52g.

1-(2-bromomethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 3.76 (3H, s), 4.71 (2H, s), 7.34 (1H, t, J=7.8Hz), 7.38 (1H, dd, J=8.0, 1.7 Hz), 7.77 (1H, dd, J=7.8, 1.7 Hz).

Reference Preparation Example 7

Anhydrous aluminium chloride 16.0 g was added to N,N-dimethylformamide180 mL under ice-cooling, and the mixtures were stirred for fifteenminutes. Thereto was added sodium azide 7.8 g and the mixtures werestirred for fifteen minutes. Thereto was then added1-methoxy-3-isocyanato-2-methylbenzene 17.0 g, and the resultingmixtures were heated at 80° C. for four and a half hours. The reactionsolutions after cooling were added to a mixture of sodium nitrite 25 g,water 2 L and ice 500 g with stirring. The mixtures were acidified with10% hydrochloric acid and were extracted with ethyl acetate. The organiclayers were washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure to give1-(2-methyl-3-methoxyphenyl)-1,4-dihydrotetrazole-5-one 16.2 g.

1-(2-methyl-3-methoxyphenyl)-1,4-dihydrotetrazole-5-one

¹H-NMR (DMSO-d₆) δ(ppm): 1.99 (3H, s), 3.87 (3H, s), 7.01 (1H, d, J=8.1Hz), 7.17 (1H, d, J=8.1 Hz). 7.36 (1H, t, J=8.3 Hz), 14.63 (1H, s).

Reference Preparation Example 8

To a mixture of 1-(2-methyl-3-methoxyphenyl)-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 7) 10.00 g andN,N-dimethylformamide 100 mL was added 60% sodium hydride 2.47 g underice-cooling. The reaction mixtures were raised to room temperature andwere stirred for fourteen hours. To the reaction mixtures was addedmethyl iodide 3.5 mL under ice-cooling. The mixtures were raised to roomtemperature and were stirred for one hour. To the reaction mixtures wasadded methyl iodide 3.5 mL under ice-cooling. The mixtures were raisedto room temperature and stirred for fourteen hours. To the reactionmixtures was added water and the mixtures were extracted with ethylacetate. The organic layers were washed with 10% hydrochloric acid,water and saturated saline, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. The resulting residues weresubjected to a silica gel column chromatography to give1-(2-methyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one 2.19 g.

1-(2-methyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹-NMR (CDCl₃) δ(ppm): 2.11 (3H, s), 3,72 (3H, s) , 3.88 (3H, s), 6.95(1H, d, J=8.2 Hz), 6.98 (1H, d, J=8.5 Hz), 7.29 (1H, t, J=8.2 Hz)

Reference Preparation Example 9

To a mixture of1-(2-methyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 8) 2.19 g,1,1′-azobis(cyclohexane-1-carbonitrile) 0.52 g, N-bromosuccinimide 2.16g and chlorobenzene 40 mL was stirred with heating under reflux for fivehours. To the reaction solutions after cooling was added water, and theresulting mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residues were subjected to a silica gel column chromatographyto give1-(2-bromomethyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one2.36 g.

1-(2-bromomethyl-3-methoxyphenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 3.74 (3H, s), 3.96 (3H, s) , 4.93 (2H, s), 7.02(1H, dd, J=1.0, 8.5 Hz), 7.04 (1H, d, J=9.0 Hz), 7.43 (1H, t, J=8.1 Hz).

Reference Preparation Example 10

A mixture of1-(2-bromomethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 6) 45.0 g, sodium methoxide37.4 g and tetrahydrofuran 600 mL was stirred at room temperature forthree hours. To the reaction mixtures was added aqueous saturated sodiumbicarbonate solution, and the resulting mixtures were extracted withethyl acetate. The organic layers were washed with aqueous saturatedsodium bicarbonate solution, and then dried over anhydrous sodiumsulfate. The mixtures were concentrated under reduced pressure to give1-(2-methoxymethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one36.2 g.

1-(2-methoxymethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 3.23 (3H, s) , 3.72 (3H, s), 4.67 (2H, s), 7.33(1H, t, J=7.8 Hz), 7.38 (1H, dd, J=1.2, 8.1 Hz), 7.76 (1H, dd, J=1.5,7.8 Hz).

Reference Preparation Example 11

A mixture of1-(2-methoxymethyl-3-bromophenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 10) 36.2 g, methylboronicacid 23.2 g, cesium fluoride 66.7 g,[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloridedichloromethane adduct 10.6 g and dioxane 500 mL was stirred at 90° C.for five and a half hours. The reaction mixtures after cooling werefiltered, and the filtrates were concentrated under reduced pressure.The resulting residues were subjected to a silica gel columnchromatography to give1-(2-methoxymethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one25.6 g.

1-(2-methoxymethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 2.48 (3H, s), 3.23 (3H, s), 3.72 (3H, s), 4.42(2H, s), 7.21 (1H, t, J=5.1 Hz), 7.35 (2H, d, J=4.8 Hz).

Reference Preparation Example 12

A mixture of1-(2-methoxymethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 11) 25.6 g, acetic acid 50mL and 25% hydrogen bromide-acetic acid solution 50 mL was stirred at65° C. for one hour. To the reaction mixtures was added saturatedsaline, and the mixtures were extracted with ethyl acetate. The organiclayers were washed with aqueous saturated sodium bicarbonate solutionand were then dried over anhydrous sodium sulfate. The mixtures wereconcentrated under reduced pressure to give1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one27.9 g.

1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one

¹H-NMR (CDCl₃) δ(ppm): 2.51 (3H, s), 3.75 (3H, s), 4.51 (2H, s),7.22-7.24 (1H, m), 7.36-7.39 (2H, m).

Reference Preparation Example 13

A mixture of1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 12) 1.0 g,1-acetyl-1H-pyrazole-3-ol 0.47 g, potassium carbonate 0.63 g andacetonitrile 20 mL was stirred with heating under reflux for two hours.To the reaction mixtures after standing to cool was added water, and theresulting mixtures were extracted with ethyl acetate. The organic layerswere washed with water and saturated saline, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresulting residue was subjected to a silica gel column chromatography togive1-(2-{[1-acetyl-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one0.58 g.

¹H-NMR (CDCl₃) δ(ppm): 8.01 (1H, d, J=2.9 Hz), 7.43-7.38 (2H, m), 7.26(1H, dd, J=6.9, 2.1 Hz), 5.88 (1H, d, J=2.9 Hz), 5.31 (2H, s), 3.69 (3H,s), 2.55 (3H, s), 2.54 (3H, s).

Reference Preparation Example 14

A mixture of1-(2-{[1-acetyl-1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one(described in Reference Preparation Example 13) 3.4 g, sodium methoxide0.59 g and methanol 30 mL was stirred at room temperature for two hours.The reaction mixtures were added to aqueous saturated sodium bicarbonatesolution, and the resulting mixtures were extracted with ethyl acetate.The organic layers were washed with water and saturated saline, driedover anhydrous magnesium sulfate, and then concentrated under reducedpressure. The resulting residue was subjected to a silica gel columnchromatography to give1-(2-{[1H-pyrazol-3-yl]oxymethyl}-3-methylphenyl)-4-methyl-1,4-dihydrotetrazole-5-one2.5 g.

¹H-NMR (CDCl₃) δ(ppm): 9.61 (1H, s), 7.40-7.35 (2H, m), 7.27 (1H, d,J=2.4 Hz), 7.24 (1H, dd, J=6.5, 2.8 Hz), 5.63 (1H, d, J=2.4 Hz), 5.23(2H, d, J=11.2 Hz), 3.66 (3H, s), 2.52 (3H, s).

The compounds selected from the present tetrazolinone compound 12 to thepresent tetrazolinone compound 81, which can be prepared according tothe above-mentioned Process A to Process C, are shown below.

TABLE 2 Present tetrazolinone compound Q R² 12 4-chlorophenyl fluoro 134-fluorophenyl chloro 14 4-methylphenyl chloro 15 4-methoxyphenyl chloro16 4-fluorophenyl bromo 17 4-methoxyphenyl bromo 18 4-chlorophenyl iodo19 phenyl methyl 20 4-fluorophenyl methyl 21 4-methylphenyl methyl 224-cyanophenyl methyl 23 4-methylthiophenyl methyl 243-fluoro-4-methoxyphenyl methyl 25 4-ethoxyphenyl methyl 263-fluoro-4-methylphenyl methyl 27 2-fluoro-4-methylphenyl methyl 284-fluorophenyl methoxy 29 4-methylphenyl methoxy 30 4-methoxyphenylmethoxy 31 4-chlorophenyl difluoromethyl 32 4-chlorophenyltrifluoromethyl 33 4-chlorophenyl 1-propenyl 34 4-chlorophenyl propyl 354-chlorophenyl isopropyl

TABLE 3 Present tetrazolinone compound Q R² 36 4-chlorophenyl ethenyl 374-chlorophenyl 2-propenyl 38 4-chlorophenyl 1-methylethenyl 394-chlorophenyl ethynyl 40 4-bromophenyl chloro 41 4-bromophenyl bromo 424-bromophenyl methoxy 43 4-trifluoromethoxyphenyl methyl 444-fluorophenyl cyclopropyl 45 4-fluorophenyl ethyl 46 4-bromophenylethyl 47 4-bromophenyl cyclopropyl 48 3-methylthiophenyl methyl 494-methoxyphenyl ethyl 50 4-methoxyphenyl cyclopropyl 51 4-methylphenylcyclopropyl 52 4-methylphenyl ethyl 53 4-methylphenyl bromo 542-methylthiophenyl methyl 55 2,3,4,5,6-pentafluorophenyl methyl 562-chlorophenyl methyl 57 4-chlorophenyl ethoxy 58 4-fluorophenyl ethoxy59 4-methoxyphenyl ethoxy

TABLE 4 Present tetrazolinone compound Q R² 60 4-bromophenyl ethoxy 61phenyl ethoxy 62 4-chlorophenyl methylthio 63 3-chlorophenyl methyl 644-nitrophenyl methyl 65 2-fluorophenyl methyl 66 2-methylphenyl methyl67 2-bromophenyl methyl 68 3-fluorophenyl methyl 69 3-methylphenylmethyl 70 3-bromophenyl methyl 71 3-methoxyphenyl methyl 722-methoxyphenyl chloro 73 2-methoxyphenyl methoxy 74 2-methoxyphenylethyl 75 2-methoxyphenyl cyclopropyl 76 4-ethylphenyl methyl 774-trifluoromethylphenyl methyl 78 5-chloro-2-methoxyphenyl methyl 792-ethoxyphenyl methyl 80 2-isopropoxyphenyl methyl 813-chloro-2-methoxyphenyl methyl

Examples of an embodiment of the present tetrazolinone compound includethe compounds represented by the formula (1) wherein the substituentsrepresent the following ones.

a tetrazolinone compound represented by the formula (1) wherein n is aninteger of any one of 0 to 2; R¹ represents a halogen atom, a C1-C6alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitrogroup or a cyano group; and R² represents a methyl group, a cyclopropylgroup, a chloro atom, a bromo atom, an ethyl group, or a methoxy group;

a tetrazolinone compound represented by the formula (1) wherein n is aninteger of any one of 0 to 2; R¹ represents a halogen atom, a methylgroup, an ethyl group, or a methoxy group; and R² represents a C1-C3alkyl group, a C3-C4 cycloalkyl group, a halogen atom, a C2-C3 alkenylgroup, a C1-C3 alkoxy group, a C1-C2 alkylthio group, or a C2-C3 alkynylgroup;

a tetrazolinone compound represented by the formula (1) wherein n is aninteger of any one of 0 to 2; R¹ represents a halogen atom, a methylgroup, an ethyl group, or a methoxy group; and R² represents a methylgroup, a cyclopropyl group, a chloro atom, a bromo atom, an ethyl group,or a methoxy group;

a tetrazolinone compound represented by the formula (1) wherein n is aninteger of any one of 0 to 2; R¹ represents a halogen atom, a C1-C6alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitrogroup, or a cyano group,

a tetrazolinone compound represented by the formula (1) wherein n is aninteger of any one of 0 to 2; and R¹ represents a halogen atom, a methylgroup, an ethyl group, or a methoxy group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogenatom, a C2-C3 alkenyl group, a C1-C3 alkoxy group, a C1-C2 alkylthiogroup, or a C2-C3 alkynyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a methyl group, a cyclopropyl group, a chloro atom, a bromoatom, an ethyl group, or a methoxy group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a C1-C3 alkyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a methyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents an ethyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a C3-C4 cycloalkyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a cyclopropyl group;

a tetrazolinone compound represented by the formula (1) wherein R²represents a halogen atom;

a tetrazolinone compound represented by the formula (1) wherein R²represents a chloro atom;

a tetrazolinone compound represented by the formula (1) wherein R²represents a bromo atom;

a tetrazolinone compound represented by the formula (1) wherein R²represents a C1-C3 alkoxy group; and

a tetrazolinone compound represented by the formula (1) wherein R²represents a methoxy group.

Examples of an embodiment of the composition of the present inventioninclude the following ones.

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, R² represents aC1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom, or a C1-C3alkoxy group, and any one of Compounds I to VI;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C3 alkoxy group, R¹ represents aC1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3alkoxy group, and any one of Compounds I to VI;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound I;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound II;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound III;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound IV;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound V;

a composition for controlling plant diseases comprising a tetrazolinonecompound represented by the formula (1) wherein n is an integer of 1 or2, R¹ represents a halogen atom or a C1-C6 alkoxy group, and R²represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atomor a C1-C3 alkoxy group, and Compound VI;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound I in the ratio of 0.1/1;

a composition for controlling plant diseases wherein comprising any oneof compounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound I in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound I in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound II in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound II in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound II in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound III in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound III in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound III in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IV in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IV in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IV in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound V in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound V in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound V in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VI in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VI in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VI in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VII in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VII in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VIII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VIII in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound VIII in the ratio of10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IX in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IX in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound IX in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound X in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound X in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound X in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XI in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XI in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XI in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XII in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XII in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIII in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIII in the ratio of10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIV in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIV in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XIV in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XV in the ratio of 0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XV in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XV in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVI in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVI in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVI in the ratio of 10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVII in the ratio of 1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVII in the ratio of10/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVIII in the ratio of0.1/1;

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVIII in the ratio of1/1; and

a composition for controlling plant diseases comprising any one ofcompounds selected from the present tetrazolinone compound 1 to thepresent tetrazolinone compound 81 and Compound XVIII in the ratio of10/1.

Next, the Formulation Examples are shown below. The term “part(s)” means“part(s) by weight”.

Formulation Example 1

Fifty (50) parts of any one of the above-mentioned composition of thepresent inventions, 3 parts of calcium lignosulfonate, 2 parts ofmagnesium lauryl sulfate and 45 parts of synthetic hydrated silicondioxide are well mixed while grinding to obtain a formulation.

Formulation Example 2

Twenty (20) parts of any one of the above-mentioned composition of thepresent inventions, 1.5 parts of sorbitan trioleate are mixed with 28.5parts of an aqueous solution containing 2 parts of polyvinyl alcohol,and the mixture is then finely-ground by a wet grinding method. To thismixture is then added 40 parts of an aqueous solution containing 0.05parts of xanthane gum and 0.1 parts of magnesium aluminium silicate, and10 parts of propylene glycol is further added thereto. The mixture isstirred to obtain a formulation.

Formulation Example 3

Two (2) parts of any one of the above-mentioned composition of thepresent inventions, 88 parts of kaolin clay and 10 parts of talc aremixed-grinding to obtain a formulation.

Formulation Example 4

Five (5) parts of any one of the above-mentioned composition of thepresent inventions, 14 parts of polyoxyethylene styryl phenyl ether, 6parts of calcium dodecylbenzene sulfonate and 75 parts of xylene aremixed-grinding to obtain a formulation.

Formulation Example 5

Two (2) parts of any one of the above-mentioned composition of thepresent inventions, one part of synthetic hydrated silicon dioxide, 2parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts ofkaolin clay are mixed-grinding and thereto is added water and themixture is well kneaded and is then granulated and dried to obtain aformulation.

Formulation Example 6

Ten (10) parts of any one of the above-mentioned composition of thepresent inventions, 35 parts of white carbon containing 50 parts ofammonium polyoxyethylene alkyl ether sulfate, and 55 parts of water aremixed, and the mixture is then finely-ground by a wet grinding method toobtain a formulation.

Next, Test examples are used to show an efficacy of the composition ofthe present invention on controlling plant diseases.

Here the control effects were evaluated by visually observing a lesionarea on the tested plants when examined and followed by comparing thelesion area of the plants treated with the composition of the presentinvention with a lesion area of the untreated plants.

The “Efficacy” in each test means a value calculated by the following“Equation 1”, and it is ranked depending on its numerical value as shownin Table 5.

Efficacy=100×(X−Y)/X   “Equation 1”

where

-   X: Degree of fungal growth in non-treated area-   Y: Degree of fungal growth in treated area

TABLE 5 Efficacy Efficacy Rank more than 95 A 80 or more to less than 95B 50 or more to less than 80 C 30 or more to less than 50 D less than 30E

Test Example 1 Control Test Against Wheat Leaf Blotch (Septoria tritici)

Each of the testing compounds was diluted with dimethyl sulfoxide (DMSO)to the prescribed concentration, respectively, and each DMSO solution ofthe testing compounds was dispensed into a titer plate (with 96 wells)in the amount of 1 μl. Thereto was then dispensed 150 μl of a potatodextrose broth to which conidia of wheat leaf blight fungus wereinoculated in advance. This plate was cultured at 18° C. for four days,thereby allowing wheat leaf blight fungus to undergo proliferation, andthe absorbance at 550 nm of each well of the titer plate was thenmeasured to determine a degree of growth of the wheat leaf blightfungus. The efficacy was calculated from the obtained degree of growthby the above-mentioned “Equation 1”, and was then ranked according to[Table 5]. The test results are shown in the following Table 6 to Table16.

TABLE 6 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 1 Present 1 Compound I 3 Atetrazolinone compound 1 Present 3 Compound II 1 A tetrazolinonecompound 1 Present 1 Compound II 3 A tetrazolinone compound 1 Present 3Compound III 1 A tetrazolinone compound 1 Present 1 Compound III 3 Atetrazolinone compound 1 Present 3 Compound IV 1 A tetrazolinonecompound 1 Present 1 Compound IV 3 A tetrazolinone compound 1 Present 3Compound V 1 A tetrazolinone compound 1 Present 1 Compound V 3 Atetrazolinone compound 1 Present 3 Compound VI 1 A tetrazolinonecompound 1 Present 1 Compound VI 3 A tetrazolinone compound 1

TABLE 7 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 2 Present 1 Compound I 3 Atetrazolinone compound 2 Present 3 Compound II 1 A tetrazolinonecompound 2 Present 1 Compound II 3 A tetrazolinone compound 2 Present 3Compound III 1 A tetrazolinone compound 2 Present 1 Compound III 3 Atetrazolinone compound 2 Present 3 Compound IV 1 A tetrazolinonecompound 2 Present 1 Compound IV 3 A tetrazolinone compound 2 Present 3Compound V 1 A tetrazolinone compound 2 Present 1 Compound V 3 Atetrazolinone compound 2 Present 3 Compound VI 1 A tetrazolinonecompound 2 Present 1 Compound VI 3 A tetrazolinone compound 2

TABLE 8 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 3 Present 1 Compound I 3 Atetrazolinone compound 3 Present 3 Compound II 1 A tetrazolinonecompound 3 Present 1 Compound II 3 A tetrazolinone compound 3 Present 3Compound III 1 A tetrazolinone compound 3 Present 1 Compound III 3 Atetrazolinone compound 3 Present 3 Compound IV 1 A tetrazolinonecompound 3 Present 1 Compound IV 3 A tetrazolinone compound 3 Present 3Compound V 1 A tetrazolinone compound 3 Present 1 Compound V 3 Atetrazolinone compound 3 Present 3 Compound VI 1 A tetrazolinonecompound 3 Present 1 Compound VI 3 A tetrazolinone compound 3

TABLE 9 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 4 Present 1 Compound I 3 Atetrazolinone compound 4 Present 3 Compound II 1 A tetrazolinonecompound 4 Present 1 Compound II 3 A tetrazolinone compound 4 Present 3Compound III 1 A tetrazolinone compound 4 Present 1 Compound III 3 Atetrazolinone compound 4 Present 3 Compound IV 1 A tetrazolinonecompound 4 Present 1 Compound IV 3 A tetrazolinone compound 4 Present 3Compound V 1 A tetrazolinone compound 4 Present 1 Compound V 3 Atetrazolinone compound 4 Present 3 Compound VI 1 A tetrazolinonecompound 4 Present 1 Compound VI 3 A tetrazolinone compound 4

TABLE 10 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 5 Present 1 Compound I 3 Atetrazolinone compound 5 Present 3 Compound II 1 A tetrazolinonecompound 5 Present 1 Compound II 3 A tetrazolinone compound 5 Present 3Compound III 1 A tetrazolinone compound 5 Present 1 Compound III 3 Atetrazolinone compound 5 Present 3 Compound IV 1 A tetrazolinonecompound 5 Present 1 Compound IV 3 A tetrazolinone compound 5 Present 3Compound V 1 A tetrazolinone compound 5 Present 1 Compound V 3 Atetrazolinone compound 5 Present 3 Compound VI 1 A tetrazolinonecompound 5 Present 1 Compound VI 3 A tetrazolinone compound 5

TABLE 11 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 6 Present 1 Compound I 3 Atetrazolinone compound 6 Present 3 Compound II 1 A tetrazolinonecompound 6 Present 1 Compound II 3 A tetrazolinone compound 6 Present 3Compound III 1 A tetrazolinone compound 6 Present 1 Compound III 3 Atetrazolinone compound 6 Present 3 Compound IV 1 A tetrazolinonecompound 6 Present 1 Compound IV 3 A tetrazolinone compound 6 Present 3Compound V 1 A tetrazolinone compound 6 Present 1 Compound V 3 Atetrazolinone compound 6 Present 3 Compound VI 1 A tetrazolinonecompound 6 Present 1 Compound VI 3 A tetrazolinone compound 6

TABLE 12 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 7 Present 1 Compound I 3 Atetrazolinone compound 7 Present 3 Compound II 1 A tetrazolinonecompound 7 Present 1 Compound II 3 A tetrazolinone compound 7 Present 3Compound III 1 A tetrazolinone compound 7 Present 1 Compound III 3 Atetrazolinone compound 7 Present 3 Compound IV 1 A tetrazolinonecompound 7 Present 1 Compound IV 3 A tetrazolinone compound 7 Present 3Compound V 1 A tetrazolinone compound 7 Present 1 Compound V 3 Atetrazolinone compound 7 Present 3 Compound VI 1 A tetrazolinonecompound 7 Present 1 Compound VI 3 A tetrazolinone compound 7

TABLE 13 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 8 Present 1 Compound I 3 Atetrazolinone compound 8 Present 3 Compound II 1 A tetrazolinonecompound 8 Present 1 Compound II 3 A tetrazolinone compound 8 Present 3Compound III 1 A tetrazolinone compound 8 Present 1 Compound III 3 Atetrazolinone compound 8 Present 3 Compound IV 1 A tetrazolinonecompound 8 Present 1 Compound IV 3 A tetrazolinone compound 8 Present 3Compound V 1 A tetrazolinone compound 8 Present 1 Compound V 3 Atetrazolinone compound 8 Present 3 Compound VI 1 A tetrazolinonecompound 8 Present 1 Compound VI 3 A tetrazolinone compound 8

TABLE 14 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 9 Present 1 Compound I 3 Atetrazolinone compound 9 Present 3 Compound II 1 A tetrazolinonecompound 9 Present 1 Compound II 3 A tetrazolinone compound 9 Present 3Compound III 1 A tetrazolinone compound 9 Present 1 Compound III 3 Atetrazolinone compound 9 Present 3 Compound IV 1 A tetrazolinonecompound 9 Present 1 Compound IV 3 A tetrazolinone compound 9 Present 3Compound V 1 A tetrazolinone compound 9 Present 1 Compound V 3 Atetrazolinone compound 9 Present 3 Compound VI 1 A tetrazolinonecompound 9 Present 1 Compound VI 3 A tetrazolinone compound 9

TABLE 15 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 10 Present 1 Compound I 3 Atetrazolinone compound 10 Present 3 Compound II 1 A tetrazolinonecompound 10 Present 1 Compound II 3 A tetrazolinone compound 10 Present3 Compound III 1 A tetrazolinone compound 10 Present 1 Compound III 3 Atetrazolinone compound 10 Present 3 Compound IV 1 A tetrazolinonecompound 10 Present 1 Compound IV 3 A tetrazolinone compound 10 Present3 Compound V 1 A tetrazolinone compound 10 Present 1 Compound V 3 Atetrazolinone compound 10 Present 3 Compound VI 1 A tetrazolinonecompound 10 Present 1 Compound VI 3 A tetrazolinone compound 10

TABLE 16 Present Concen- Present Concen- tetrazolinone trationcarboxamide tration Efficacy compound (ppm) compound (ppm) Rank Present3 Compound I 1 A tetrazolinone compound 11 Present 1 Compound I 3 Atetrazolinone compound 11 Present 3 Compound II 1 A tetrazolinonecompound 11 Present 1 Compound II 3 A tetrazolinone compound 11 Present3 Compound III 1 A tetrazolinone compound 11 Present 1 Compound III 3 Atetrazolinone compound 11 Present 3 Compound IV 1 A tetrazolinonecompound 11 Present 1 Compound IV 3 A tetrazolinone compound 11 Present3 Compound V 1 A tetrazolinone compound 11 Present 1 Compound V 3 Atetrazolinone compound 11 Present 3 Compound VI 1 A tetrazolinonecompound 11 Present 1 Compound VI 3 A tetrazolinone compound 11

INDUSTRIAL APPLICABILITY

The present invention can control plant diseases.

1. A composition for controlling plant diseases comprising atetrazolinone compound represented by a formula (1):

wherein n is an integer of any one of 0 to 5; R¹ represents a halogenatom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthiogroup, a nitro group or a cyano group; R² represents a C1-C3 alkylgroup, a C3-C4 cycloalkyl group, a halogen atom, a C1-C3 alkoxy group, aC1-C2 alkylthio group, a C2-C3 alkenyl group, or a C2-C3 alkynyl group,the R¹ or R² can have independently halogen atom(s) in the alkyl moiety;with the proviso that when n is an integer of 2 or more, two or more ofthe R¹ may be different from each other, and one or more carboxamidecompounds selected from the Group (A): Group (A): a group consisting ofbixafen, benzovindiflupyr, fluxapyroxad, penthiopyrad,N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylicacid amide, a compound represented by the following formula (b):

isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen,flutolanil, mepronil, carboxin, thifluzamide, and furametpyr.
 2. Thecomposition for controlling plant diseases according to claim 1 whereina weight ratio of the tetrazolinone compound to the carboxamide compoundis that of the tetrazolinone compound/the carboxamide compound=0.1/1 to10/1.
 3. A method for controlling plant diseases which comprisesapplying each effective amount of a tetrazolinone compound representedby a formula (1):

wherein n is an integer of any one of 0 to 5; R¹ represents a halogenatom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthiogroup, a nitro group or a cyano group; R² represents a C1-C3 alkylgroup, a C3-C4 cycloalkyl group, a halogen atom, a C1-C3 alkoxy group, aC1-C2 alkylthio group, a C2-C3 alkenyl group, or a C2-C3 alkynyl group,the R¹ or R² can have independently halogen atom(s) in the alkyl moiety;with the proviso that when n is an integer of 2 or more, two or more ofthe R¹ may be different from each other, and one or more carboxamidecompounds selected from the Group (A): Group (A): a group consisting ofbixafen, benzovindiflupyr, fluxapyroxad, penthiopyrad,N-(1,1,3-trimethylindan-4-yl)-1-methyl-3-difluoromethylpyrazole-4-carboxylicacid amide, a compound represented by the following formula (b):

isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen,flutolanil, mepronil, carboxin, thifluzamide, and furametpyr, to a plantor a soil for cultivating the plant.
 4. The method for controlling plantdiseases according to claim 3 wherein a weight ratiot of thetetrazolinone compound to the carboxamide compound is that of thetetrazolinone compound/the carboxamide compound=0.1/1 to 10/1.
 5. Themethod for controlling plant diseases according to claim 3 wherein theplant or the soil for cultivating the plant is wheat or the soil forcultivating wheat, respectively.